EP0021939B1 - Hydrazino (or azido) 5-alkylthio pyrimidines, processes for their preparation and their uses as herbicides and fongicides - Google Patents

Hydrazino (or azido) 5-alkylthio pyrimidines, processes for their preparation and their uses as herbicides and fongicides Download PDF

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Publication number
EP0021939B1
EP0021939B1 EP19800400830 EP80400830A EP0021939B1 EP 0021939 B1 EP0021939 B1 EP 0021939B1 EP 19800400830 EP19800400830 EP 19800400830 EP 80400830 A EP80400830 A EP 80400830A EP 0021939 B1 EP0021939 B1 EP 0021939B1
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Prior art keywords
formula
hydrazino
group
compounds
pyrimidine
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EP19800400830
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German (de)
French (fr)
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EP0021939A1 (en
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Daniel Henry Balde
Gérard Emile Marcel Boutemy
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Produits Chimiques Ugine Kuhlmann
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Produits Chimiques Ugine Kuhlmann
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms

Definitions

  • the present invention relates to novel 5-alkylthio-pyrimidines carrying a hydrazino, substituted hydrazino or azido group, their methods of preparation and their uses as herbicides and fungicides.
  • the new 5-alkylthio pyrimidines according to the invention can be represented by the general formula: wherein R 1 is an alkyl group having 1 to 5 carbon atoms, one of the substituents X and Y is a chlorine atom or a group wherein R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or benzyl, and the other is a azido group, hydrazino, or a substituted hydrazino group corresponding to one of the formulas in which R 4 and R s are alkyl groups having 1 to 5 carbon atoms, or the substituents X and Y are identical and then represent azido, hydrazino, or hydrazino substituted groups of formula formulas in which R 4 and R 5 have the abovementioned meanings.
  • the present invention relates to the compounds of formula (I) as a whole, it relates more particularly to those of these compounds for which R 1 is a methyl group, one of the substituents X and Y is a chlorine atom or one amino group, methylamino and the other is an azido, hydrazino group, or the two substituents X and Y are hydrazino groups.
  • the latter can, for example, be heated to a temperature of 10 ° C to 100 ° C in an acid medium in the presence of a nitrite of an alkali or alkaline earth metal.
  • the nitrous acid necessary for the reaction is produced by the action of the acid on the nitrite.
  • an acid medium mention may be made in particular of mixed water + acetic acid media.
  • Reaction of compounds of formula (I) having one or two hydrazino substituents with the chloroformate of formula can be carried out for example at a temperature of 0 ° C to 20 ° C, in the presence of a solvent and a base to fix the hydrochloric acid released. It is convenient to operate within the pyridine which serves as both solvent and base.
  • Reaction of compounds of formula (I) having one or two hydrazino substituents with the ketone can be carried out for example by refluxing said compounds within the ketone.
  • the compounds of formula (I) in which one of the substituents X and Y is a chlorine atom or a group and the other is a hydrazino group can be prepared by condensation of one mole of hydrazine with one mole of a 2,4,4,6-alkylthio-pyrimidine trichloro of formula (II) and condensation, mole to mole, of dichloro-4,6 (or -2,6) hydrazino-2 (or -4) alkyl t hio-5 pyrimidine of formula (III) or (III) bis) thus boiling the solvent used. It is advantageously carried out at a temperature of 5 ° C to 25 ° C.
  • R 1 , R 2 and R 3 have the same meanings as in formula (1).
  • m is a number greater than 0 and less than 1.
  • reaction (1) The mixture of compounds (III) and (III bis) obtained in reaction (1) can also be subjected to the second stage of the process (reaction with compound IV). A mixture of the two isomeric compounds of position (I) and (1) bis is then obtained, a mixture which can be used as it is in herbicide and fungicide applications.
  • the condensation reactions (1), (2) and (2a) can be carried out in an aqueous medium, in an organic solvent medium or else in a mixed water + organic solvent medium.
  • organic solvents which can be used mention may in particular be made of benzene and toluene.
  • condensation reactions (1), (2) and (2) bis are carried out in the presence of a basic agent capable of fixing the hydrochloric acid formed in the reaction.
  • This basic agent can be hydrazine itself or the compound of formula (IV) itself in the case of reactions (1) and (2) or (2a) respectively.
  • the quantity of hydrazine used to carry out the reaction (1) is the stoichiometric quantity, that is to say 1 mole per mole of compound (II) in the case where the basic agent used to fix HCI is other that the hydrazine itself and 2 moles per mole of compound (II) in the case of the basic agent used to fix HCl is hydrazine itself.
  • Reaction (1) can be carried out at a temperature ranging from 0 ° C to the boiling point of the solvent used. It is advantageously carried out at a temperature of 5 ° C to 25 ° C.
  • Reactions (2) and (2) bis cannot be carried out at temperatures as low as those usable for reaction (1). They are generally carried out between 100 and 150 ° C, possibly under a pressure higher than atmospheric pressure if the nature of the solvent used requires it.
  • the compounds of formula (I) in which one of the substituents X and Y is a group and the other is a hydrazino group can also be prepared by condensation, mole to mole, of hydrazine with a compound of formula (V) or (V bis), according to the reaction scheme:
  • the condensation reactions (3) and (3a) can be carried out in an aqueous medium, in an organic solvent medium or else in a mixed water + organic solvent medium. They are carried out at a temperature ranging from 25 ° C. to the boiling point of the solvent used and in the presence of a basic agent capable of fixing the hydrochloric acid formed in the reaction.
  • Reaction (4) is carried out under the same conditions as reaction (1), except as regards the quantity of hydrazine involved. To carry out reaction (4), an quantity of hydrazine greater than the stoichiometric quantity.
  • the compounds of formula (I) are herbicides active in pre- and post-emergence treatments. They have the property of destroying a large number of undesirable plants, particularly those belonging to the dicotyledon class, often at doses less than or equal to 2,500 g / ha. In addition, at the doses at which they are active with respect to undesirable plants, the compounds of formula (1) frequently exhibit zero or very low phytotoxicity with regard to cereals such as wheat and corn.
  • the herbicidal compounds according to the invention can be incorporated, jointly with other herbicides or separately, in formulations which contain, in addition to the active material, the inert additives usually used in agriculture to facilitate the conservation, the implementation in aqueous suspension, adhesion to the foliage and resistance to atmospheric agents and biological degradation (hence greater persistence of the action), such as solid diluents (talc, silica, kieselguhr, clay, etc.) .) or liquids (mineral oils, water, organic solvents such as ketones, alcohols, hydrocarbons or their chlorine derivatives), adjuvants, surfactants, antioxidants. and stabilizers.
  • Such formulations can be in the form of wettable powders, solutions emulsifiable in water, suspensions, granules or any other form in use in the field of herbicides.
  • the content of compounds of formula (I) can vary from 1% to 95% by weight.
  • the content of compounds according to the invention can vary from 1% to 80% by weight, that in other herbicides from 80% to 1% by weight, the complement to 100% being constituted by inert additives.
  • trichloro-2 is dispersed by stirring in 500 ml of water containing 1.2 g of PLURONIC L 92 (non-ionic surfactant consisting of a copolymer of ethylene oxide and propylene oxide) , 4.6 5-methylthio pyrimidine finely ground. Then, in 10 minutes, 170 g of a 20% aqueous ammonia solution, maintaining the temperature at 5 ° C. It is then left overnight at room temperature, then the precipitate formed is filtered and washed with water.
  • PLURONIC L 92 non-ionic surfactant consisting of a copolymer of ethylene oxide and propylene oxide
  • the precipitate a (weight 6 g) consists essentially of the compound 4,6-dichloro-2 amino-5-methylthio pyrimidine.
  • the precipitate c (weight 17.2 g) consists of the compound 2,6-dichloro-4 amino-5-methylthio pyrimidine.
  • the structure of the product obtained is confirmed by its infrared and R.M.N.
  • the compounds according to the invention are formulated in the form of aqueous suspensions containing 5% of a surfactant called "TWEEN 20".
  • the suspensions are applied on day D by spraying, either on plants 10 days old, which makes it possible to study the post-emergence action of the products, or on seeds deposited on the soil surface, which allows study the pre-emergence action. These seeds are covered with 2 cm of soil just after application.
  • the plants and seeds are placed in 18 x 12 x 5 cm plastic containers filled with standard soil made up of 3 parts of sand, 1 part of potting soil and 1 part of clay. After treatment, the containers are placed on an automatic irrigation tablet in a greenhouse maintained at 22 ° C and a humidity rate of 70%.
  • the plants tested are TRITICUM SP wheat, PHASEOLUS SP beans, BETA SP beet, SINAPIS SP mustard, TARAXACUM SP dandelion and ZEA SP corn.
  • the herbicidal efficacy of the compounds according to the invention with regard to the plants tested is expressed by a figure which represents the percentage of destruction of the plants in the treated batches. This percentage is evaluated by taking as a reference the plants from untreated control lots. The number 0 therefore indicates that the condition of the plants is the same in the treated lots and in the control lots, the number 100 that the plants are completely destroyed in the treated lots, which corresponds to maximum efficiency.
  • Example 12 The tests are carried out as in Example 12 with the following doses of the compound of Example 6 (2-methylamino-6-chloro-4-azido-5-methylthio-pyrimidine):
  • Fungicidal activity of the compounds (mycelial growth inhibition test).
  • the nutritive medium used is the Czapeck medium of the following composition:
  • aqueous suspension of the compound to be tested is incorporated into this medium, which is kept in fusion at 45 ° C., at the rate of one ml of aqueous suspension for 9 ml of Czapeck medium.
  • the concentration of compound in the aqueous suspension is such that the final concentration of compound in the nutrient medium is 100 ppm.
  • the medium is then poured into 90 mm diameter petri dishes and allowed to cool and solidify. Each can is contaminated with fragments of mycelium collected from eight day old mushroom cultures. These mushrooms are spasarium roseum, rhizoctonia solani and alternaria tenuis.
  • the plates are incubated for 2 days in a chamber maintained at 22 ° C and at a humidity rate of 70%. After these 2 days, the mycelium developed, forming around the point of contamination of the circular mycelial areas, the diameter of which is measured.
  • Example -14 The same nutritive medium is used as in Example -14 (Czapeck agar medium) and the compound to be tested is incorporated therein in the same way.
  • the final concentration of compound in the nutrient medium is 100 ppm.
  • the medium thus treated is poured into the cells of the ceramics plates and allowed to cool and solidify.
  • the lenses of nutrient medium are contaminated by depositing on each 50 ⁇ l of an aqueous suspension of spores of the species botrytis cinerea, alternaria tenuis, aspergilus niger, penicillium expansum.
  • the ceramics are placed in 15 cm diameter petri dishes lined with damp filter paper at the bottom. It is incubated for 24 hours at a temperature of 22 ° C. After which the number of non-germinated spores is counted under the microscope and compared with the total number of spores.
  • the compound to be tested is formulated in the form of an aqueous suspension whose concentration of compound is 1000 ppm. This suspension is sprayed on the leaves of 10-day-old “Rika” barley plants or 20-day-old “Marmande” tomato plants or "12-day-old full basket” bean plants, grown in pots. The quantity of suspension provided per unit area of the pots is equivalent to 1000 1 / ha.
  • the barley leaves are sprinkled with Erisiphe graminis spores, an aqueous suspension of Phytophtora infestans spores is sprayed on the foliage-tomatoes and an aqueous spore suspension is sprayed on the bean leaves 'Uromyces phaseoli.
  • the plants are then left in the greenhouse at 22 ° C.
  • Example 16 The procedure is as in Example 16, with aqueous suspensions whose concentration of compound is respectively 1000 ppm, 250 ppm, 62.5 ppm and 15.6 ppm.
  • Table VII The results obtained, collated in Table VII below, are translated by a figure which represents the level of contamination of the treated plants expressed as a percentage of the level of contamination of the control plants. 0 therefore means that no powdery mildew has developed, 100 that the level of contamination is identical to that of the control plants.
  • Example 5 The compound of Example 5, applied preventively, exerts a fungicidal effect on the powdery mildew of barley.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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Description

La présente invention a pour objet de nouvelles alkylthio-5 pyrimidines portant un groupe hydrazino, hydrazino substitué ou azido, leurs procédés de préparation et leurs utilisations en tant que herbicides et fongicides.The present invention relates to novel 5-alkylthio-pyrimidines carrying a hydrazino, substituted hydrazino or azido group, their methods of preparation and their uses as herbicides and fungicides.

Il est déjà connu, par les brevets français 2 031 422, 2 317 291, 2 137 933, 2 119 234, par l'article de MOSSINI, MAGGIALI, BRANCA Ateano Parmense, Acta Nat., 14 (1978), 119-126, et par la demande de brevet européen 78 400062.2 publiée sous le numéro 0 000 681, des dérivés de la pyrimidine herbicides, mais ces dérivés ne portent jamais simultanément un groupe alkylthio en position 5 et un groupe hydrazino, hydrazino substitué ou azido.It is already known from French patents 2,031,422, 2,317,291, 2,137,933, 2,119,234, from the article by MOSSINI, MAGGIALI, BRANCA Ateano Parmense, Acta Nat., 14 (1978), 119-126 , and by European patent application 78 400062.2 published under the number 0 000 681, herbicide pyrimidine derivatives, but these derivatives never simultaneously carry an alkylthio group in position 5 and a hydrazino, substituted hydrazino or azido group.

Les nouvelles alkylthio-5 pyrimidines selon l'invention peuvent être représentées par la formule générale:

Figure imgb0001
dans laquelle R1 est un groupe alkyle ayant 1 à 5 atomes de carbone, l'un des substituants X et Y est un atome de chlore ou un groupe
Figure imgb0002
dans lequel R2 est un atome d'hydrogène ou un groupe alkyle ayant 1 à 5 atomes de carbone et R3 est un atome d'hydrogène ou un groupe alkyle ayant 1 à 5 atomes de carbone ou benzyle, et l'autre est un groupe azido, hydrazino, ou un groupe hydrazino substitué répondant à l'une des formules
Figure imgb0003
dans lesquelles R4 et Rs sont des groupes alkyle ayant 1 à 5 atomes de carbone, ou bien les substituants X et Y sont identiques et représentent alors des groupes azido, hydrazino, ou hydrazino substitués de formule
Figure imgb0004
formules dans lesquelles R4 et R5 ont les significations précitées.The new 5-alkylthio pyrimidines according to the invention can be represented by the general formula:
Figure imgb0001
 wherein R 1 is an alkyl group having 1 to 5 carbon atoms, one of the substituents X and Y is a chlorine atom or a group
Figure imgb0002
 wherein R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or benzyl, and the other is a azido group, hydrazino, or a substituted hydrazino group corresponding to one of the formulas
Figure imgb0003
 in which R 4 and R s are alkyl groups having 1 to 5 carbon atoms, or the substituents X and Y are identical and then represent azido, hydrazino, or hydrazino substituted groups of formula
Figure imgb0004
 formulas in which R 4 and R 5 have the abovementioned meanings.

Bien que la présente invention concerne les composés de formule (I) dans leur ensemble, elle a plus particulièrement pour objet ceux de ces composés pour lesquels R1 est un groupe méthyle, l'un des substituants X et Y est un atome de chlore ou un groupe amino, méthylamino et l'autre est un groupe azido, hydrazino,

Figure imgb0005
ou bien les deux substituants X et Y sont des groupes hydrazino.Although the present invention relates to the compounds of formula (I) as a whole, it relates more particularly to those of these compounds for which R 1 is a methyl group, one of the substituents X and Y is a chlorine atom or one amino group, methylamino and the other is an azido, hydrazino group,
Figure imgb0005
 or the two substituents X and Y are hydrazino groups.

Les composés de formule (1) dans lesquels l'un au moins des substituants X et Y est un groupe azido ou un groupe hydrazino substitué de formule

Figure imgb0006
peuvent être préparés par action, sur le composé de formule (1) correspondant dans lequel ledit substituant ou lesdits substituants sont des groupes hydrazino, de respectivement l'acide nitreux, un chloroformiate de formule
Figure imgb0007
un isocyanate de formule R4-N=C=O, une cétone de formule
Figure imgb0008
 The compounds of formula (1) in which at least one of the substituents X and Y is an azido group or a substituted hydrazino group of formula
Figure imgb0006
 may be prepared by action, on the corresponding compound of formula (1) in which said substituent or said substituents are hydrazino groups, respectively nitrous acid, a chloroformate of formula
Figure imgb0007
 an isocyanate of formula R 4 -N = C = O, a ketone of formula
Figure imgb0008

Pour préparer les composés de formule (1) ayant un ou deux substituants azido par action de l'acide nitreux sur les composés correspondants de formule (1) ayant un ou deux substituants hydrazino, on peut par exemple chauffer ces derniers à une température de 10°C à 100°C en milieu acide en présence d'un nitrite d'un métal alcalin ou alcalino-terreux. L'acide nitreux nécessaire à la réaction est produit par l'action de l'acide sur le nitrite. Comme milieu acide on peut citer en particulier les milieux mixtes eau + acide acétique.To prepare the compounds of formula (1) having one or two azido substituents by the action of nitrous acid on the corresponding compounds of formula (1) having one or two hydrazino substituents, the latter can, for example, be heated to a temperature of 10 ° C to 100 ° C in an acid medium in the presence of a nitrite of an alkali or alkaline earth metal. The nitrous acid necessary for the reaction is produced by the action of the acid on the nitrite. As an acid medium, mention may be made in particular of mixed water + acetic acid media.

La réaction des composés de formule (I) ayant un ou deux substituants hydrazino avec le chloroformiate de formule

Figure imgb0009
peut être effectuée par exemple à une température de 0°C à 20°C, en présence d'un solvant et d'une base pour fixer l'acide chlorhydrique libéré. Il est commode d'opérer au sein de la pyridine qui sert à la fois de solvant et de base.Reaction of compounds of formula (I) having one or two hydrazino substituents with the chloroformate of formula
Figure imgb0009
 can be carried out for example at a temperature of 0 ° C to 20 ° C, in the presence of a solvent and a base to fix the hydrochloric acid released. It is convenient to operate within the pyridine which serves as both solvent and base.

La réaction des composés de formule (I) ayant un ou deux substituants hydrazino avec l'isocyanate R4-N=C=O peut être effectuée dans un solvant inerte vis-à-vis de l'isocyanate, par exemple le tétrahydrofuranne, à une température allant de 20°C jusqu'à la température d'ébullition du solvant.The reaction of the compounds of formula (I) having one or two hydrazino substituents with the isocyanate R 4- N = C = O can be carried out in a solvent inert with respect to the isocyanate, for example tetrahydrofuran, with a temperature ranging from 20 ° C to the boiling point of the solvent.

La réaction des composés de formule (I) ayant un ou deux substituants hydrazino avec la cétone

Figure imgb0010
peut être effectuée par exemple en chauffant au reflux lesdits composés au sein de la cétone.Reaction of compounds of formula (I) having one or two hydrazino substituents with the ketone
Figure imgb0010
 can be carried out for example by refluxing said compounds within the ketone.

Les composés de formule (I) dans lesquels l'un des substituants X et Y est un atome de chlore ou un groupe

Figure imgb0011
et l'autre est un groupe hydrazino peuvent être préparés par condensation d'une mole d'hydrazine avec une mole d'une trichloro-2,4,6 alkylthio-5 pyrimidine de formule (II) et condensation, mole à mole, de la dichloro-4,6 (ou -2,6) hydrazino-2 (ou -4) alkylthio-5 pyrimidine de formule (III) ou (III) bis) ainsi d'ébullition du solvant utilisé. Elle est effectuée avantageusement à une température de 5°C à 25°C.
Figure imgb0012
Figure imgb0013
Figure imgb0014
 The compounds of formula (I) in which one of the substituents X and Y is a chlorine atom or a group
Figure imgb0011
 and the other is a hydrazino group can be prepared by condensation of one mole of hydrazine with one mole of a 2,4,4,6-alkylthio-pyrimidine trichloro of formula (II) and condensation, mole to mole, of dichloro-4,6 (or -2,6) hydrazino-2 (or -4) alkyl t hio-5 pyrimidine of formula (III) or (III) bis) thus boiling the solvent used. It is advantageously carried out at a temperature of 5 ° C to 25 ° C.
Figure imgb0012
Figure imgb0013
Figure imgb0014

Dans les formules (II) à (IV), R1, R2 et R3 ont les mêmes significations que dans la formule (1). m est un nombre supérieur à 0 et inférieur à 1.In formulas (II) to (IV), R 1 , R 2 and R 3 have the same meanings as in formula (1). m is a number greater than 0 and less than 1.

La trichloro-2,4,6 méthylthio-5 pyrimidine,'produit de formule (II) pour lequel R1 =CH3, est un composé connu, qui a été décrit par exemple dans le brevet français 1 549 494. Les autres composés de formule (II) peuvent être préparés par le procédé général décrit dans ce brevet.2,4,6,6-methylthio-pyrimidine trichloro, product of formula (II) for which R 1 = CH 3 , is a known compound, which has been described for example in French patent 1,549,494. The other compounds of formula (II) can be prepared by the general process described in this patent.

On peut aussi soumettre le mélange des composés (III) et (III bis) obtenu dans la réaction (1) à la deuxième étape du procédé (réaction avec le composé IV). On obtient alors un mélange des deux composés isomères de position (I) et (1) bis, mélange qui peut être employé tel quel dans les applications herbicides et fongicides.The mixture of compounds (III) and (III bis) obtained in reaction (1) can also be subjected to the second stage of the process (reaction with compound IV). A mixture of the two isomeric compounds of position (I) and (1) bis is then obtained, a mixture which can be used as it is in herbicide and fungicide applications.

Les réactions de condensation (1), (2) et (2 bis) peuvent être effectuées en milieu aqueux, en milieu solvant organique ou encore en milieu mixte eau + solvant organique. Comme solvants organiques utilisables on peut citer en particulier le benzène et le toluène.The condensation reactions (1), (2) and (2a) can be carried out in an aqueous medium, in an organic solvent medium or else in a mixed water + organic solvent medium. As organic solvents which can be used, mention may in particular be made of benzene and toluene.

Les réactions de condensation (1), (2) et (2) bis sont effectuées en présence d'un agent basique susceptible de fixer l'acide chlorhydrique formé dans la réaction. Cet agent basique peut être l'hydrazine elle-même.ou le composé de formule (IV) lui-même dans le cas respectivement des réactions (1) et (2) ou (2 bis).The condensation reactions (1), (2) and (2) bis are carried out in the presence of a basic agent capable of fixing the hydrochloric acid formed in the reaction. This basic agent can be hydrazine itself or the compound of formula (IV) itself in the case of reactions (1) and (2) or (2a) respectively.

La quantité d'hydrazine mise en jeu pour effectuer la réaction (1 ) est la quantité stoechiométrique, c'est-à-dire 1 mole par mole de composé (II) dans le cas où l'agent basique utilisé pour fixer HCI est autre que l'hydrazine elle-même et 2 moles par mole de composé (II) dans le cas du l'agent basique utilisé pour fixer HCl est l'hydrazine elle-même.The quantity of hydrazine used to carry out the reaction (1) is the stoichiometric quantity, that is to say 1 mole per mole of compound (II) in the case where the basic agent used to fix HCI is other that the hydrazine itself and 2 moles per mole of compound (II) in the case of the basic agent used to fix HCl is hydrazine itself.

La réaction (1) peut être réalisée à une température allant de 0°C jusqu'à la température d'ébullition du solvent utilisé. Elle est effectuée avantageusement à une température de 5°C à 25°C. Les réactions (2) et (2) bis ne peuvent être réalisées à des températures aussi basses que celles utilisables pour la réaction (1). Elles sont effectuées en général entre 100 et 150°C, éventuellement sous une pression supérieure à la pression atmosphérique si la nature du solvant utilisé l'exige.Reaction (1) can be carried out at a temperature ranging from 0 ° C to the boiling point of the solvent used. It is advantageously carried out at a temperature of 5 ° C to 25 ° C. Reactions (2) and (2) bis cannot be carried out at temperatures as low as those usable for reaction (1). They are generally carried out between 100 and 150 ° C, possibly under a pressure higher than atmospheric pressure if the nature of the solvent used requires it.

Les composés de formule (I) dans lesquels l'un des substituants X et Y est un groupe

Figure imgb0015
et l'autre est un groupe hydrazino peuvent aussi être préparés par condensation, mole à mole, de l'hydrazine avec un composé de formule (V) ou (V bis), suivant le schéma réactionnel:
Figure imgb0016
Figure imgb0017
 The compounds of formula (I) in which one of the substituents X and Y is a group
Figure imgb0015
 and the other is a hydrazino group can also be prepared by condensation, mole to mole, of hydrazine with a compound of formula (V) or (V bis), according to the reaction scheme:
Figure imgb0016
Figure imgb0017

On peut également soumettre le mélange des composés (V) et (V bis) résultant de la condensation mole à mole de la trichloro-2,4,6 alkylthio-5 pyrimidine de formule (II) avec un composé de formule

Figure imgb0018
à la réaction de condensation avec l'hydrazine. On obtient alors un mélange des deux composés isomères de position (1 ter) et (I quart), mélange qui peut être employé tel quel dans les applications herbicides et fongicides.It is also possible to subject the mixture of the compounds (V) and (V bis) resulting from the mole to mole condensation of the 2,4,4,6-alkylthio-pyrimidine trichloro of formula (II) with a compound of formula
Figure imgb0018
 to the condensation reaction with hydrazine. A mixture of the two isomeric compounds of position (1 ter) and (I quarter) is then obtained, a mixture which can be used as it is in herbicide and fungicide applications.

La préparation des composés de formules (V) et (V) bis et des mélanges de composés isomères correspondants a été décrite en particulier dans les brevets français 2 1 1 9 234, 2 173 746, 2 257 294 et 2 281 117.The preparation of the compounds of formulas (V) and (V) bis and of the mixtures of corresponding isomeric compounds has been described in particular in French patents 2 1 1 9 234, 2 173 746, 2 257 294 and 2 281 117.

Les réactions de condensation (3) et (3 bis) peuvent être effectuées en milieu aqueux, en milieu solvant organique ou encore en milieu mixte eau + solvant organique. Elles sont effectuées à une température allant de 25°C à la température d'ébullition du solvant utilisé et en présence d'un agent basique susceptible de fixer l'acide chlorhydrique formé dans la réaction.The condensation reactions (3) and (3a) can be carried out in an aqueous medium, in an organic solvent medium or else in a mixed water + organic solvent medium. They are carried out at a temperature ranging from 25 ° C. to the boiling point of the solvent used and in the presence of a basic agent capable of fixing the hydrochloric acid formed in the reaction.

Enfin les composés de formule (I) pour lesquels X et Y sont tous les deux des groupes hydrazino peuvent être préparés, en une seule étape, par condensation de l'hydrazine avec une trichloro-2,4,6 alkylthio-5 pyrimidine de formule (II) suivant le schéma réactionnel:

Figure imgb0019
Finally, the compounds of formula (I) for which X and Y are both hydrazino groups can be prepared, in a single step, by condensation of the hydrazine with a 2,4,4,6-trichloro-5-alkylthio pyrimidine of formula (II) according to the reaction scheme:
Figure imgb0019

La réaction (4) est effectuée dans les mêmes conditions que la réaction (1), sauf en ce qui concerne la quantité d'hydrazine mise en jeu. Pour effectuer la réaction (4) on met en jeu une quantité d'hydrazine supérieure à la quantité stoechiométrique.Reaction (4) is carried out under the same conditions as reaction (1), except as regards the quantity of hydrazine involved. To carry out reaction (4), an quantity of hydrazine greater than the stoichiometric quantity.

Les composés de formule (I) sont des herbicides actifs dans les traitements de pré- et post-levée. Ils ont la propriété de détruire un grand nombre de plantes indésirables appartement en particulier à la classe des dicotylédones et ce souvent à des doses inférieures ou égales à 2 500 g/ha. En outre, aux doses auxquelles ils sont actifs vis-à-vis des plantes indésirables, les composés de formule (1) présentent fréquemment une phytotoxicité nulle ou très faible vis-à-vis de céréales telles que le blé et le maïs.The compounds of formula (I) are herbicides active in pre- and post-emergence treatments. They have the property of destroying a large number of undesirable plants, particularly those belonging to the dicotyledon class, often at doses less than or equal to 2,500 g / ha. In addition, at the doses at which they are active with respect to undesirable plants, the compounds of formula (1) frequently exhibit zero or very low phytotoxicity with regard to cereals such as wheat and corn.

Pour leur misé en oeuvre les composés herbicides selon l'invention peuvent être incorporés, conjointement avec d'autres herbicides ou séparément, dans des formulations qui contiennent, outre la matière active, les additifs inertes habituellement utilisés en agriculture pour faciliter la conservation, la mise en suspension aqueuse, l'adhérence sur le feuillage et la résistance aux agents atmosphériques et aux dégradations biologiques (d'où une persistance plus grande de l'action), tels que diluants solides (talc, silice, kieselguhr, argile, etc...) ou liquides (huiles minérales, eau, solvants organiques comme par exemple des cétones, des alcools, des hydrocarbures ou leurs dérives chlorés), adjuvants, tensio-actifs, antioxydants. et stabilisants. De telles formulations peuvent se présenter sous la forme de poudres mouillables, solutions émulsifiables dans l'eau, suspensions, granulés ou toute autre forme en usage dans le domaine des herbicides.For their use, the herbicidal compounds according to the invention can be incorporated, jointly with other herbicides or separately, in formulations which contain, in addition to the active material, the inert additives usually used in agriculture to facilitate the conservation, the implementation in aqueous suspension, adhesion to the foliage and resistance to atmospheric agents and biological degradation (hence greater persistence of the action), such as solid diluents (talc, silica, kieselguhr, clay, etc.) .) or liquids (mineral oils, water, organic solvents such as ketones, alcohols, hydrocarbons or their chlorine derivatives), adjuvants, surfactants, antioxidants. and stabilizers. Such formulations can be in the form of wettable powders, solutions emulsifiable in water, suspensions, granules or any other form in use in the field of herbicides.

Dans les formulations contenant seulement des composés herbicides selon l'invention et des additifs inertes, la teneur en composés de formule (I) (matière active) peut varier de 1 % à 95% en poids. Dans les formulations contenant des composés herbicides selon l'invention, d'autres herbicides et des additifs inertes, la teneur en composés selon l'invention peut varier de 1 % à 80% en poids, celle en herbicides autres de 80% à 1 % en poids, le complément à 100% étant constitué par les additifs inertes.In formulations containing only herbicidal compounds according to the invention and inert additives, the content of compounds of formula (I) (active material) can vary from 1% to 95% by weight. In the formulations containing herbicidal compounds according to the invention, other herbicides and inert additives, the content of compounds according to the invention can vary from 1% to 80% by weight, that in other herbicides from 80% to 1% by weight, the complement to 100% being constituted by inert additives.

En outre certains des composés de formule (1) possèdent des propriétés fongicides.In addition, some of the compounds of formula (1) have fungicidal properties.

Les exemples suivants illustrent l'invention sans la limiter. Les données relatives aux spectres de résonance magnétique nucléaire (spectres R.M.N.) figurant dans ces exemples ont été obtenues en mettant les produits en solution dans le diméthylsulfoxyde deutéré.The following examples illustrate the invention without limiting it. The data relating to the nuclear magnetic resonance spectra (R.M.N. spectra) appearing in these examples were obtained by putting the products in solution in deuterated dimethylsulfoxide.

Exemple 1Example 1

Préparation d'un mélange des deux isomères dichloro-4,6 hydrazino-2 méthylthio-5 pyrimidine et dichloro-2,6 hydrazino-4 méthylthio-5 pyrimidine.Preparation of a mixture of the two isomers 4,6-dichloro-2-hydrazino-5-methylthio pyrimidine and 2,6-dichloro-4-hydrazino-5-methylthio-pyrimidine.

Dans un réacteur maintenu à 5°C et contenant 120 g de toluène et 46 g de trichloro-2,4,6 méthylthio-5 pyrimidine on introduit 65 g d'une solution aqueuse à 32,3% d'hydrate d'hydrazine. On laisse réagir 3 heures à 5°C, puis une nuit à 20°C. On filtre le précipité obtenu, le lave et le sèche. On obtient ainsi 40,5 g (ce qui correspond à un rendement de 90%) d'un produit constitué par un mélange de dichloro-4,6 hydrazino-2 méthylthio-5 pyrimidine et dichloro-2,6 hydrazino-4 méthylthio-5 pyrimidine.In a reactor maintained at 5 ° C and containing 120 g of toluene and 46 g of 2,4,4,6-trichloro-5-methylthio pyrimidine are introduced 65 g of an aqueous solution containing 32.3% of hydrazine hydrate. It is left to react for 3 hours at 5 ° C., then overnight at 20 ° C. The precipitate obtained is filtered, washed and dried. 40.5 g are thus obtained (which corresponds to a yield of 90%) of a product consisting of a mixture of 4,6-dichloro-2-hydrazino-5-methylthio pyrimidine and 2,6-dichloro-4-hydrazino-methylthio- 5 pyrimidine.

Point de fusion du mélange: 150-152°C (avec décomposition).Melting point of the mixture: 150-152 ° C (with decomposition).

Spectre R.M.N. du produit obtenu:

  • Les déplacements chimiques 3 sont les suivants:
    Figure imgb0020
NMR spectrum of the product obtained:
  • The chemical shifts 3 are as follows:
    Figure imgb0020

Exemple 2Example 2

Préparation d'un mélange des deux isomères amino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine et amino-4 chloro-6 hydrazino-2 méthylthio-5 pyrimidine.Preparation of a mixture of the two isomers 2-amino-6-chloro-4-hydrazino-5-methylthio-pyrimidine and 4-amino-chloro-6-hydrazino-2-methylthio-5-pyrimidine.

1èra étape1st stage

Dans 500 ml d'eau contenant 1,2 g de PLURONIC L 92 (agent tensio-actif non ionique constitué par un copolymère d'oxyde d'éthylène et d'oxyde de propyléne) on disperse par agitation 46 .g de trichloro-2,4,6 méthylthio-5 pyrimidine finement broyée. Puis on introduit en 10 minutes 170 g d'une solution aqueuse d'ammoniac à 20%, en maintenant la température à 5°C. On laisse ensuite une nuit à la température ambiante, puis on filtre le précipité formé et le lave à l'eau. On recueille ainsi 42 g d'un produit qui est un mélange des deux composés isomères dichloro-4,6 amino-2 méthylthio-5 pyrimidine et dichloro-2,6 amino-4 méthylthio-5 pyrimidine (mélange dénommé D par la suite).In 46 ml of trichloro-2 is dispersed by stirring in 500 ml of water containing 1.2 g of PLURONIC L 92 (non-ionic surfactant consisting of a copolymer of ethylene oxide and propylene oxide) , 4.6 5-methylthio pyrimidine finely ground. Then, in 10 minutes, 170 g of a 20% aqueous ammonia solution, maintaining the temperature at 5 ° C. It is then left overnight at room temperature, then the precipitate formed is filtered and washed with water. 42 g of a product are thus collected, which is a mixture of the two isomeric compounds 4,6-dichloro-2-amino-5-methylthio-pyrimidine and 2,6-dichloro-4-amino-4-methylthio-5-pyrimidine (mixture called D below) .

2ème étape2nd stage

Dans un réacteur contenant 100 ml de toluène et 7 g du mélange D on introduit 155 g d'une solution aqueuse à 32,3% d'hydrate d'hydrazine. On laisse réagir 7 heurs à 25°C, puis on filtre le précipité obtenu, le lave à l'eau et le sèche. On obtient ainsi 6 g (ce qui correspond à un rendement de 88,4%) d'un produit constitué par un mélange d'amino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine et d'amino-4 chloro-6 hydrazino-2 méthylthio-5 pyrimidine. Ce mélange fond à 170°C (avec décomposition).155 g of a 32.3% aqueous solution of hydrazine hydrate are introduced into a reactor containing 100 ml of toluene and 7 g of mixture D. It is left to react for 7 hours at 25 ° C., then the precipitate obtained is filtered, washed with water and dried. 6 g are thus obtained (which corresponds to a yield of 88.4%) of a product consisting of a mixture of 2-amino-6-chloro-4 hydrazino-5-methylthio pyrimidine and 4-amino-chloro-6 2-hydrazino-5-methylthio pyrimidine. This mixture melts at 170 ° C (with decomposition).

Spectre R.M.N. du produit obtenu:Spectrum R.M.N. of the product obtained:

Figure imgb0021
Figure imgb0021

Exemple 3Example 3

Préparation de l'amino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine et de l'amino-4 chloro-6 hydrazino-2 méthylthio-5 pyrimidine.Preparation of 2 amino-chloro-6 hydrazino-4 methylthio-5 pyrimidine and amino-4 chloro-6 hydrazino-2 methylthio-5 pyrimidine.

40 g du mélange D obtenu dans la lère étape de l'exemple 2 sont dissous dans 700 ml d'acide chlorhydrique concentré. A la solution obtenue on ajoute 200 ml d'eau. Il se forme un précipité a que l'on sépare par filtration. On ajoute au filtrat 120 ml d'eau. Il se forme un nouveau précipité b que l'on sépare par filtration. On ajoute enfin au filtrat 260 ml d'eau puis 200 ml d'une solution

Figure imgb0022
d'hydroxyde de sodium. Il se forme un précipité c que l'on sépare par filtration.40 g of mixture D obtained in the 1st step of Example 2 are dissolved in 700 ml of concentrated hydrochloric acid. To the solution obtained is added 200 ml of water. A precipitate is formed which is separated by filtration. 120 ml of water are added to the filtrate. A new precipitate b is formed which is separated by filtration. Finally, 260 ml of water and then 200 ml of a solution are added to the filtrate.
Figure imgb0022
 sodium hydroxide. A precipitate c is formed which is separated by filtration.

Le précipité a (poids 6 g) est constitué essentiellement du composé dichloro-4,6 amino-2 méthylthio-5 pyrimidine. Le précipité c (poids 17,2 g) est constitué du composé dichloro-2,6 amino-4 méthylthio-5 pyrimidine.The precipitate a (weight 6 g) consists essentially of the compound 4,6-dichloro-2 amino-5-methylthio pyrimidine. The precipitate c (weight 17.2 g) consists of the compound 2,6-dichloro-4 amino-5-methylthio pyrimidine.

En remplaçant dans la deuxième étape de l'exemple 2 les 7 g de mélangé D par respectivement 7 g du précipité a et 7 g du précipité c, on obtient l'amino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine et l'amino-4 chloro-6 hydrazino-2 méthylthio-5 pyrimidine.By replacing, in the second step of Example 2, the 7 g of mixture D with respectively 7 g of precipitate a and 7 g of precipitate c, 2-chloro-6-chloro-4-hydrazino-methylthio-pyrimidine and l are obtained. 4-amino-6-chloro-2-hydrazino-5-methylthio pyrimidine.

Exemple 4Example 4

Préparation de la méthylamino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine.Preparation of 2-methylamino-6 chloro-4-hydrazino-methylthio-5 pyrimidine.

Dans un réacteur, muni d'un agitateur, on introduit 500 ml de benzène, 500 ml d'eau, 44,8 g de dichloro-4,6 méthylamino-2 méthylthio-5 pyrimidine et 30 g d'hydrate d'hydrazine. On chauffe au reflux pendant 3 heures sous bonne agitation, puis on refroidit et filtre le précipité obtenu. Le précipité est ensuite lavé à l'eau, puis au méthanol et est séché. On obtient ainsi 23 g (ce qui correspond à un rendement de 52,3%) de méthylamino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine qui fond à 176°C (avec décomposition).500 ml of benzene, 500 ml of water, 44.8 g of 2, 4-methylamino-5-methylthio-pyrimidine and 30 g of hydrazine hydrate are introduced into a reactor equipped with an agitator. The mixture is heated at reflux for 3 hours with good stirring, then cooled and the precipitate obtained is filtered. The precipitate is then washed with water, then with methanol and is dried. 23 g are thus obtained (which corresponds to a yield of 52.3%) of 2-methylamino-6 chloro-4-hydrazino-methylthio-5 pyrimidine which melts at 176 ° C. (with decomposition).

Analyse élémentaire:Elementary analysis:

Figure imgb0023
Figure imgb0023

Exemple 5Example 5

Préparation d'un mélange des deux isomères amino-2 chloro-6 (méthoxycarbonyl-2) hydrazino-4 méthylthio-5 pyrimidine et amino-4 chloro-6 (méthoxycarbonyi-2) hydrazino-2 méthylthio-5 pyrimidine.Preparation of a mixture of the two 2-amino isomers chloro-6 (methoxycarbonyl-2) hydrazino-4 methylthio-5 pyrimidine and amino-4 chloro-6 (methoxycarbonyi-2) hydrazino-2 methylthio-5 pyrimidine.

Dans un réacteur contenant 160 ml de pyridinè et 20,55 g du produit obtenu à la 2ème étape de l'exemple 2 on introduit 10,3 g de chloroformiate de méthyle, en maintenant la température à 0°C. On laisse réagir 4 heures à 0°C, puis 15 heures-à 20°C. On élimine ensuite la pyridine par distillation sous vide. Le résidu obtenu est lavé à l'eau et séché. On obtient ainsi 8 g (ce qui correspond à un rendement de 30,3%) d'un produit constitué par un mélange d'amino-2 chloro-6 (méthoxycarbonyl-2) hydrazino-4 méthylthio-5 pyrimidine et d'amino-4 chloro-6 (rTiéthoxycarbonyl-2) hydrazino-2 méthylthio-5 pyrimidine. Ce mélange fond à 208°C.10.3 g of methyl chloroformate are introduced into a reactor containing 160 ml of pyridine and 20.55 g of the product obtained in the second step of Example 2, while maintaining the temperature at 0 ° C. It is left to react for 4 hours at 0 ° C., then 15 hours at 20 ° C. The pyridine is then removed by vacuum distillation. The residue obtained is washed with water and dried. 8 g are thus obtained (which corresponds to a yield of 30.3%) of a product consisting of a mixture of 2-amino-chloro-6 (2-methoxycarbonyl) hydrazino-4 methylthio-5 pyrimidine and amino -4 chloro-6 (r T iethoxycarbonyl-2) hydrazino-2 methylthio-5 pyrimidine. This mixture melts at 208 ° C.

Spectre infra-rouge du produit obtenu:

  • bande d'absorption de CO à 1 700 cm-1
Infrared spectrum of the product obtained:
  • CO absorption band at 1,700 cm -1

Spectre R.M.N. du produit obtenu:

Figure imgb0024
NMR spectrum of the product obtained:
Figure imgb0024

Exemple 6Example 6

Préparation de la méthylamino-2 chloro-6 azido-4 méthylthio-5 pyrimidine.Preparation of 2-methylamino-6-chloro-4-azido-5-methylthio-pyrimidine.

Dans un réacteur contenant 85 ml d'eau, 430 ml d'acide acétique et 30 g de méthylamino-2 chloro-6 hydrazino-4 méthyithio-5 pyrimidine (préparée comme indiqué à l'exemple 4) on introduit lentement, à la température ambiante (20°C à 25°C), 17* g de nitrite de sodium. On chauffe ensuité le mélange à 50°C et maintient cette température pendant 4 heures. Puis on amène à sec, lave à l'eau le résidu obtenu et le sèche. On obtient ainsi 10 g d'un produit brut. Pour purifier ce produit, on le dissout dans un mélange de 150 ml d'acide chlorhydrique concentré et 50 ml d'eau, puis fait reprécipiter par addition de 300 ml d'eau. On obtient ainsi 4,2 g de méthylamino-2 chloro-6 azido-4 méthylthio-5 pyrimidine, qui fond à 142-144°C.In a reactor containing 85 ml of water, 430 ml of acetic acid and 30 g of 2-methylamino-6-chloro-4-hydrazino-5-methyl-pyrimidine (prepared as indicated in example 4) are introduced slowly, at the temperature ambient (20 ° C to 25 ° C), 17 * g of sodium nitrite. The mixture is then heated to 50 ° C and maintained at this temperature for 4 hours. Then it is brought to dryness, the residue obtained is washed with water and dried. 10 g of a crude product are thus obtained. To purify this product, it is dissolved in a mixture of 150 ml of concentrated hydrochloric acid and 50 ml of water, then reprecipitated by addition of 300 ml of water. 4.2 g of 2-methylamino-6-chloro-4-azido-5-methylthio-pyrimidine are thus obtained, which melts at 142-144 ° C.

Analyse élémentaire:Elementary analysis:

Figure imgb0025
Figure imgb0025

Exemple 7Example 7

Préparation d'un mélange des deux isomères amino-2 chloro-6 (méthyl-4 semicarbazido)-4 méthylthio-5 pyrimidine et amino-4 chloro-6 (méthyl-4 semicarbazido)-2 méthylthio-5 pyrimidine.Preparation of a mixture of the two isomers 2-amino chloro-6 (4-methyl semicarbazido) -4 methylthio-5 pyrimidine and amino-4 chloro-6 (4-methyl semicarbazido) -2 methylthio-5 pyrimidine.

Dans un réacteur muni d'un agitateur on introduit 35 ml de tétrahydrofuranne, 4,1 g du produit obtenu à la 2ème étape de l'exemple 2 et 1,26 g d'isocyanate de méthyle. On laisse réagir à 20°C pendant 15 heures, puis à l'ébullition pendant 2 heures. On filtre après refroidissement. On obtient ainsi 4,6 g (ce qui correspond à un rendement de 87,5%) d'un produit constitué par un mélange d'amino-2 chloro-6 (méthyl-4 semicarbazido)-4 méthylthio-5 pyrimidine et d'amino-4 chloro-6 (méthyl-4 semicarbazido)-2 méthylthio-5 pyrimidine, qui fond à 217°C.35 ml of tetrahydrofuran, 4.1 g of the product obtained in the 2nd step of Example 2 and 1.26 g of methyl isocyanate are introduced into a reactor fitted with an agitator. It is left to react at 20 ° C. for 15 hours, then at boiling for 2 hours. Filter after cooling. This gives 4.6 g (which corresponds to a yield of 87.5%) of a product consisting of a mixture of 2-amino-chloro-6 (4-methyl semicarbazido) -4 methylthio-5 pyrimidine and d amino-4 chloro-6 (4-methyl semicarbazido) -2 methylthio-5 pyrimidine, which melts at 217 ° C.

Spectre infra-rouge du produit obtenu:

  • bande d'absorption de CO à 1630 cm-1
Infrared spectrum of the product obtained:
  • CO absorption band at 1630 cm-1

Spectre R.M.N. du produit obtenu:

Figure imgb0026
NMR spectrum of the product obtained:
Figure imgb0026

Exemple 8Example 8

Préparation de la bis(hydrazino)-2,4 chloro-6 méthylthio-5 pyrimidine.Preparation of bis (hydrazino) -2,4 6-chloro-5-methylthio pyrimidine.

Dans un réacteur contenant 100 ml de toluène et 7,5 g de trichloro-2,4,6 méthylthio-5 pyrimidine on introduit 155 g d'une solution aqueuse à 32,3% d'hydrate d'hydrazine. On laisse réagir 24 heures à 20°C puis on filtré. Le précipité obtenu est lavé à l'eau et séché. On obtient ainsi 5,9 g de bis(hydrazino)-2,4 chloro-6 méthylthio-5 pyrimidine (ce qui correspond à un rendement de 81,9%)155 g of a 32.3% hydrazine hydrate solution are introduced into a reactor containing 100 ml of toluene and 7.5 g of 2,4,6,6-trichloro-5-methylthio pyrimidine. It is left to react for 24 hours at 20 ° C. and then filtered. The precipitate obtained is washed with water and dried. 5.9 g of bis (hydrazino) -2.4 6-chloro-5-methylthio-pyrimidine are thus obtained (which corresponds to a yield of 81.9%)

Exemple 9Example 9

Préparation de la benzylamino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine.Preparation of 2-benzylamino-6-chloro-4-hydrazino-5-methylthio pyrimidine.

Dans un réacteur contenant 23 g de trichloro-2,4,6 méthylthio-5 pyrimidine, 74 g de méthyléthylcétone et 65 g de glace, on coule en 30 minutes 10, 7 g de benzylamine. Puis on ajoute, à la température de 20°C, en l'espace d'une heure, une solution de 4 g d'hydroxyde de sodium dans 15 ml d'eau. On agite pendant 6 heures, puis on filtre et lave le précipité obtenu avec de la méthyléthylcétone. On obtient ainsi 10 g de benzylamino-2 dichloro-4,6 méthylthio-5 pyrimidine.10.7 g of benzylamine are poured in 30 minutes into a reactor containing 23 g of 2,4,6,6-methylthio-pyrimidine trichloro, 74 g of methyl ethyl ketone and 65 g of ice. Then a solution of 4 g of sodium hydroxide in 15 ml of water is added at a temperature of 20 ° C. over the course of an hour. The mixture is stirred for 6 hours, then filtered and the precipitate obtained is washed with methyl ethyl ketone. 10 g of 2-benzylamino-4,6-dichloro-5-methylthio-pyrimidine are thus obtained.

On fait réagir pendant 3 heures à l'ébullition, dans un milieu constitué de 85 ml de benzène et 85 m d'eau, les 10 g de benzylamino-2 dichloro-4,6 méthylthio-5 pyrimidine obtenus précédemment avec 5 g d'hydrate d'hydrazine. On filtre et lave le précipité obtenu à l'eau, puis au méthanol. On obtient ainsi 4,8 g (ce qui correspond à un rendement de 48,7%) de benzylamino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine.The 10 g of 2-benzylamino-4,6-dichloro-5,6-methylthio-pyrimidine obtained previously with 5 g of are reacted for 3 hours at boiling, in a medium consisting of 85 ml of benzene and 85 m of water hydrazine hydrate. The precipitate obtained is filtered and washed with water, then with methanol. 4.8 g are thus obtained (which corresponds to a yield of 48.7%) of 2-benzylamino-6-chloro-4-hydrazino-5-methylthio-pyrimidine.

Exemple 10 'Example 10 '

Préparation de la méthylamino-2 chloro-6 (isopropylidène-2 hydrazino)-4 méthylthio-5 pyrimidine.Preparation of 2-methylamino-chloro-6 (isopropylidene-2 hydrazino) -4 methylthio-5 pyrimidine.

On chauffe au reflux pendant 2 heures 13,2 g de méthylamino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine (préparée comme indiqué à l'exemple 4) avec 200 ml d'acétone pure. Après refroidissement, on filtre le précipité formé. On obtient ainsi 8 g de méthylamino-2 chloro-6 (isopropylidène-2 hydrazino)-4 méthylthio-5 pyrimidine, qui fond à 190°C.13.2 g of 2-methylamino-6-chloro-4-hydrazino-5-methylthio-pyrimidine (prepared as indicated in Example 4) are heated to reflux for 2 hours with 200 ml of pure acetone. After cooling, the precipitate formed is filtered. 8 g of methylamino-2 chloro-6 (isopropylidene-2 hydrazino) -4 methylthio-5 pyrimidine are thus obtained, which melts at 190 ° C.

Analyse élémentaire du produit obtenu:Elementary analysis of the product obtained:

Figure imgb0027
Figure imgb0027

La structure du produit obtenu est confirmé par ses spectres infra-rouge et R.M.N.The structure of the product obtained is confirmed by its infrared and R.M.N.

Exemple 11Example 11

Préparation d'un mélange d'amino-2 chloro-6 azido-4 méthyithio-5 pyrimidine et d'amino-4 chloro-6 azido-2 méthylthio-5 pyrimidine.Preparation of a mixture of 2-amino-chloro-6 azido-4 methyl-5-pyrimidine and amino-4 chloro-6 azido-2-methylthio-5 pyrimidine.

Dans un réacteur de 1 litre contenant 90 ml d'eau, 450 ml d'acide acétique et 30,8 g du mélange d'amino-2 chloro-6 hydrazino-4 méthylthio-5 pyrimidine et d'amino-4 chloro-6 hydrazino-2 méthylthio-5 pyrimidine obtenu à la 2ème étape de l'exemple 2, on introduit lentement, à la température ambiante (20°C à 25°C), 18,6 g de nitrite de sodium. On chauffe ensuite le mélange à 50°C et maintient cette température pendant 4 heures. Puis on amène à sec, lave à l'eau le résidu obtenu et le sèche. On obtient ainsi 16 g d'un mélange d'isomères contenant environ 30% d'amino-2 azido-4 chloro-6 méthylthio-5 pyrimidine et 70% d'amino-4 azido-2 chloro-6 méthylthio-5 pyrimidine. Ce mélange fond à 117°C.In a 1 liter reactor containing 90 ml of water, 450 ml of acetic acid and 30.8 g of the mixture of 2-amino-6-chloro-4 hydrazino-5 methylthio pyrimidine and 4-amino-chloro-6 2-hydrazino-5-methylthio pyrimidine obtained in the 2nd step of Example 2, 18.6 g of sodium nitrite are slowly introduced at room temperature (20 ° C. to 25 ° C.). The mixture is then heated to 50 ° C and maintained at this temperature for 4 hours. Then it is brought to dryness, the residue obtained is washed with water and dried. 16 g of a mixture of isomers containing about 30% 2-amino-4-azido-6-chloro-5-methylthio-pyrimidine and 70% of 4-amino-azido-2-chloro-6-methylthio-5-pyrimidine are thus obtained. This mixture melts at 117 ° C.

Spectre infra-rouge du produit obtenu:

  • bande d'absorption de N3 à 2 140 cm-1
Infrared spectrum of the product obtained:
  • absorption band from N 3 to 2 140 cm- 1

Spectre R.M.N. du produit obtenu:

  • SCHg : δ = 2,15 ppm et 2,45 ppm
NMR spectrum of the product obtained:
  • SCHg: δ = 2.15 ppm and 2.45 ppm

Exemple 12Example 12

Activité herbicide des composésHerbicidal activity of the compounds

Les composés selon l'invention sont formulés sous forme de suspensions aqueuses contenant 5% d'un tensio-actif dénommé "TWEEN 20".The compounds according to the invention are formulated in the form of aqueous suspensions containing 5% of a surfactant called "TWEEN 20".

Les quantités de suspensions appliquées équivalent à 1 000 1/ha, et les dilutions réalisées sont calculées de façon à apporter les quantités de matière active suivantes:

Figure imgb0028
The quantities of suspensions applied are equivalent to 1000 1 / ha, and the dilutions carried out are calculated so as to provide the following quantities of active material:
Figure imgb0028

Les suspensions sont appliquées au jour J. par pulvérisation, soit sur plantes âgées de 10 jours, ce qui permet d'étudier l'action de poste-levée des produits, soit sur semences déposées à la surface du sol, ce qui permet d'étudier l'action de pré-levée. Ces semences sont recouvertes de 2 cm de terre juste après l'application.The suspensions are applied on day D by spraying, either on plants 10 days old, which makes it possible to study the post-emergence action of the products, or on seeds deposited on the soil surface, which allows study the pre-emergence action. These seeds are covered with 2 cm of soil just after application.

Les plantes et graines sont disposées dans des conteneurs en plastique de 18 x 12 x 5 cm remplis d'une terre standard composée de 3 parties de sable, 1 partie de terreau et 1 partie d'argile. Après traitement, les conteneurs sont disposés sur une tablette à irrigation automatique dans une serre maintenue à 22°C et à un taux d'hygrométrie de 70%.The plants and seeds are placed in 18 x 12 x 5 cm plastic containers filled with standard soil made up of 3 parts of sand, 1 part of potting soil and 1 part of clay. After treatment, the containers are placed on an automatic irrigation tablet in a greenhouse maintained at 22 ° C and a humidity rate of 70%.

Les plantes soumises aux essais sont le blé TRITICUM SP, le haricot PHASEOLUS SP, la betterave BETA SP, la moutarde SINAPIS SP, le pissenlit TARAXACUM SP et le maïs ZEA SP.The plants tested are TRITICUM SP wheat, PHASEOLUS SP beans, BETA SP beet, SINAPIS SP mustard, TARAXACUM SP dandelion and ZEA SP corn.

On relève les résultats 14 jours après le traitement dans le cas dés traitements de post-levée et 21 jours après le traitement dans le cas des traitements de pré-levée.The results are noted 14 days after the treatment in the case of post-emergence treatments and 21 days after the treatment in the case of the pre-emergence treatments.

Les résultats relatifs aux composés des exemples 1, 2, 5, 8, 10 et 11 sont rassemblés dans le tableau n° 1.The results relating to the compounds of Examples 1, 2, 5, 8, 10 and 11 are collated in Table No. 1.

Dans ce tableau l'efficacité herbicide des composés selon l'invention vis-à-vis des plantes testées est exprimée par un chiffre qui représente le pourcentage de destruction des plantes dans les lots traités. Ce pourcentage est évalué en prenant comme référence les plantes de lots témoins non traités. Le chiffre 0 indique donc que l'état des plantes est le même dans les lots traités et dans les lots témoins, le chiffre 100 que les plantes sont entièrement détruites dans les lots traités, ce qui correspond à l'efficacité maximum.In this table, the herbicidal efficacy of the compounds according to the invention with regard to the plants tested is expressed by a figure which represents the percentage of destruction of the plants in the treated batches. This percentage is evaluated by taking as a reference the plants from untreated control lots. The number 0 therefore indicates that the condition of the plants is the same in the treated lots and in the control lots, the number 100 that the plants are completely destroyed in the treated lots, which corresponds to maximum efficiency.

Exemple 13Example 13 Activité herbicide des composésHerbicidal activity of the compounds

On conduit les essais comme à l'exemple 12 avec les doses suivantes du composé de l'exemple 6 (méthylamino-2 chloro-6 azido-4 méthylthio-5 pyrimidine):

Figure imgb0029
The tests are carried out as in Example 12 with the following doses of the compound of Example 6 (2-methylamino-6-chloro-4-azido-5-methylthio-pyrimidine):
Figure imgb0029

Les traitements sont uniquement des traitements de post-levée. Les notations sont effectuées 7, 14 et 21 jours après le traitement Les résultats obtenus sont rassemblés dans le tableau II. Dans ce tableau figurent aussi les résultats relatifs à un herbicide de référence (chlortoluron).

Figure imgb0030
Figure imgb0031
 The treatments are only post-emergence treatments. The ratings are made 7, 14 and 21 days after the treatment. The results obtained are collated in Table II. This table also shows the results for a reference herbicide (chlortoluron).
Figure imgb0030
Figure imgb0031

Exemple 14Example 14

Activité fongicide des composés (test d'inhibition de la croissance mycélienne).Fungicidal activity of the compounds (mycelial growth inhibition test).

Le milieu nutritif utilisé est le milieu Czapeck de composition suivante:

Figure imgb0032
The nutritive medium used is the Czapeck medium of the following composition:
Figure imgb0032

Une suspension aqueuse du composé à tester est incorporée dans ce milieu maintenu en fusion à 45°C, à raison d'un ml de suspension aqueuse pour 9 ml de milieu Czapeck. La concentration en composé de la suspension aqueuse est telle que la concentration finale en composé dans le milieu nutritif est 100 ppm.An aqueous suspension of the compound to be tested is incorporated into this medium, which is kept in fusion at 45 ° C., at the rate of one ml of aqueous suspension for 9 ml of Czapeck medium. The concentration of compound in the aqueous suspension is such that the final concentration of compound in the nutrient medium is 100 ppm.

Le milieu est ensuite coulé dans des boîtes de Pétri de 90 mm de diamètre et on le laisse refroidir et solidifier. Chaque boîte est contaminée à l'aide de fragments de mycélium prélevés dans des cultures de champignons âgées de huit jours. Ces champignons sont füsarium roseum, rhizoctonia solani et alternaria tenuis.The medium is then poured into 90 mm diameter petri dishes and allowed to cool and solidify. Each can is contaminated with fragments of mycelium collected from eight day old mushroom cultures. These mushrooms are füsarium roseum, rhizoctonia solani and alternaria tenuis.

On met les boîtes à incuber pendant 2 jours dans une chambre maintenue à 22°C et à un taux d'hygrométrie de 70%. Après ces 2 jours, le mycélium s'est développé réalisant autour du point de contamination des plages mycéliennes circulaires dont on mesure le diamètre.The plates are incubated for 2 days in a chamber maintained at 22 ° C and at a humidity rate of 70%. After these 2 days, the mycelium developed, forming around the point of contamination of the circular mycelial areas, the diameter of which is measured.

Les résultats obtenus avec le composé de l'exemple 1 sont présentés dans le tableau IV. Dans ce tableau le pouvoir d'inhibition de la croissance mycélienne est traduit par une note (0,2 ou 4). La note 0 correspond à une inhibition nulle (dans ce cas le diamètre des plages mycéliennes dans les boîtes contenant le milieu nitritif traité avec le composé à tester est le même que le diamètre des plages mycéliennes dans les boîtes témoins contenant le milieu nutritif non traité). La note 2 correspond à une inhibition partielle, la note 4 à une inhibition totale. Dans le tableau IV sont donnés également les résultats obtenus avec un fongicide de référence (Thirame).

Figure imgb0033
The results obtained with the compound of Example 1 are presented in Table IV. In this table the power of inhibition of mycelial growth is expressed by a note (0.2 or 4). Note 0 corresponds to zero inhibition (in this case the diameter of the mycelial areas in the dishes containing the nitritive medium treated with the test compound is the same as the diameter of the mycelial areas in the control boxes containing the untreated nutritive medium) . Note 2 corresponds to partial inhibition, note 4 to total inhibition. In Table IV are also given the results obtained with a reference fungicide (Thirame).
Figure imgb0033

Exemplè 15Example 15

Activité fongicide des composés (test d'inhibition de la germination des spores).Fungicidal activity of the compounds (test for inhibition of spore germination).

On utilise le même milieu nutritif que dans l'exemple -14 (milieu gélosé Czapeck) et on y incorpore le composé à tester de la même façon. La concentration finale en composé dans le milieu nutritif est 100 ppm.The same nutritive medium is used as in Example -14 (Czapeck agar medium) and the compound to be tested is incorporated therein in the same way. The final concentration of compound in the nutrient medium is 100 ppm.

Le milieu ainsi traité est coulé dans les alvéoles de plaques de ciréra et on laisse refroidir et solidifier. On contamine les lentilles de milieu nutritif en déposant sur chacune 50 ,ul d'une suspension aqueuse de spores des espèces botrytis cinerea, alternaria tenuis, aspergilus niger, penicillium expansum. On met les plaques de ciréra dans des boîtes de Pétri de 15 cm de diamètre garnies au fond d'un papier filtre humide. On laisse incuber 24 heures à la température de 22°C. Après quoi, on compte, sous le microscope, le nombre de spores non germées et on compare ce nombre au nombre total de spores.The medium thus treated is poured into the cells of the ceramics plates and allowed to cool and solidify. The lenses of nutrient medium are contaminated by depositing on each 50 μl of an aqueous suspension of spores of the species botrytis cinerea, alternaria tenuis, aspergilus niger, penicillium expansum. The ceramics are placed in 15 cm diameter petri dishes lined with damp filter paper at the bottom. It is incubated for 24 hours at a temperature of 22 ° C. After which the number of non-germinated spores is counted under the microscope and compared with the total number of spores.

Les résultats obtenus avec les composés des exemples 1 et 11 et un fongicide de référence (Thirame) sont présentés dans le tableau V. Dans ce tableau le pouvoir d'inhibition de la germination des spores est exprimé suivant le système de notation indiqué à l'exemple 14 (note 0,2 ou 4).

Figure imgb0034
The results obtained with the compounds of Examples 1 and 11 and a reference fungicide (Thirame) are presented in Table V. In this table, the power to inhibit the germination of spores is expressed according to the notation system indicated in example 14 (note 0.2 or 4).
Figure imgb0034

Exemple 16Example 16

Activité fongicide des composés (test in vivo sur Erisiphe graminis, Phytophtora infestans et Uromyces Phaseoli).Fungicidal activity of the compounds (in vivo test on Erisiphe graminis, Phytophtora infestans and Uromyces Phaseoli).

Le composé à tester est formulé sous forme d'une suspension aqueuse dont la concentration en composé est 1 000 ppm. Cette suspension est pulvérisée sur les feuilles de plants d'orge "Rika" âgés de 10 jours ou de plants de tomate "Marmande" âgés de 20 jours ou de plants de haricot "Mange tout plein le panier" âgés de 12 jours, cultivés en pots. La quantité de suspension apportée par unité de surface des pots équivaut à 1 000 1/ha.The compound to be tested is formulated in the form of an aqueous suspension whose concentration of compound is 1000 ppm. This suspension is sprayed on the leaves of 10-day-old "Rika" barley plants or 20-day-old "Marmande" tomato plants or "12-day-old full basket" bean plants, grown in pots. The quantity of suspension provided per unit area of the pots is equivalent to 1000 1 / ha.

24 heures après le traitement, on saupoudre sur le feuillage des orges des spores d'Erisiphe graminis, on pulvérise sur le feuillage-des tomates une suspension aqueuse de spores de Phytophtora infestans et on pulvérise sur le feuillage des haricots une suspension aqueuse de spores d'Uromyces phaseoli. On laisse ensuite les plantes en serre à 22°C.24 hours after the treatment, the barley leaves are sprinkled with Erisiphe graminis spores, an aqueous suspension of Phytophtora infestans spores is sprayed on the foliage-tomatoes and an aqueous spore suspension is sprayed on the bean leaves 'Uromyces phaseoli. The plants are then left in the greenhouse at 22 ° C.

6 jours après la contamination dans le cas des orges, 5 jours après la contamination dans le cas des tomates et 10 jours après la contamination dans le cas des haricots, on note le nombre de taches d'oïdium, de mildiou ou de rouille présentes sur les feuilles et on compare ce nombre à celui obtenu dans le cas des plantes témoins (c'est-à-dire des plantes non traitées avec le composé, mais contaminées). Les résultats sont exprimés suivant l'échelle de notation suivante:6 days after contamination in the case of barley, 5 days after contamination in the case of tomatoes and 10 days after contamination in the case of beans, note the number of stains of powdery mildew, mildew or rust present on the leaves and this number is compared to that obtained in the case of control plants (that is to say plants not treated with the compound, but contaminated). The results are expressed according to the following grading scale:

Figure imgb0035
Figure imgb0035

Les résultats obtenus avec les composés des exemples 1 et 5 et les fongicides de référence Manèbe et triadiméfon sont rassemblés dans le tableau VI ci-après.

Figure imgb0036
The results obtained with the compounds of Examples 1 and 5 and the reference fungicides Maneb and triadimefon are collated in Table VI below.
Figure imgb0036

Exemple 17Example 17

Activité fongicide des composés (test in vivo sur Erisiphe graminis).Fungicidal activity of the compounds (in vivo test on Erisiphe graminis).

On opère comme à l'exemple 16, avec des suspensions aqueuses dont la concentration en composé est respectivement 1 000 ppm, 250 ppm, 62,5 ppm et 15,6 ppm. Les résultats obtenus, rassemblés dans le tableau VII ci-après, sont traduits par un chiffre qui représente le niveau de contamination des plantes traitées exprimé en pourcentage du niveau de contamination des plantes témoins. 0 signifie donc qu'aucune tache d'oïdium ne s'est développée, 100 que lé niveau de contamination est identique à celui des plantes témoins.

Figure imgb0037
The procedure is as in Example 16, with aqueous suspensions whose concentration of compound is respectively 1000 ppm, 250 ppm, 62.5 ppm and 15.6 ppm. The results obtained, collated in Table VII below, are translated by a figure which represents the level of contamination of the treated plants expressed as a percentage of the level of contamination of the control plants. 0 therefore means that no powdery mildew has developed, 100 that the level of contamination is identical to that of the control plants.
Figure imgb0037

Le composé de l'exemple 5, appliqué préventivement, exerce un effet fongicide sur l'oïdium de l'orge.The compound of Example 5, applied preventively, exerts a fungicidal effect on the powdery mildew of barley.

Claims (10)

1. Compounds of the formula:
Figure imgb0066
in which R1 is an alkyl group having 1 to 5 carbon atoms, one of the substituents X and Y is a chlorine atom or an
Figure imgb0067
group in which R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R3 is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, or benzyl, and the other is an azido or hydrazino group, or a substituted hydrazino group corresponding to one of the formulae:
Figure imgb0068
 in which R4 and R5 are alkyl groups having 1 to 5 carbon atoms, or else the substituents X and Y are identical and: thus represent azido, hydrazino or substituted hydrazino groups with the formula
Figure imgb0069
in which R4 and R5 have the significance g.iven above.
2. Compounds according to claim 1 in which R1 is a methyl group, one of the substituents X and Y is a chlorine atom or an amino or methylamino group and the other is an azido, hydrazino,
Figure imgb0070
group or else the two substituents X and Y are hydrazino groups..
3. Mixtures of position isomeric compounds corresponding to the. formula (I) of claim 1.
4. Process for the preparation of compounds of formula (I) of claim 1 in which at least one of the substituents X and Y is an azido group, or a substituted hydrazino group of formula
Figure imgb0071
characterised in that the compound corresponding to formula (1) in which at least one of the substituents X and Y is a hydrazino group is reacted with, respectively, nitrous acid, a chloroformate of formula.
Figure imgb0072
an isocyanate of formula R4-N=C=O, a ketone of formula
Figure imgb0073
5. Process for the preparation of compounds of formula (I) of claim 1 in which one of the substituents X and Y is a chlorine atom or an
Figure imgb0074
group and the other is a hydrazino group characterised in that one mole of hydrazine is condensed with one mole of a 2,4,6-trichloro-5-alkylthio pyrimidine of formula:
Figure imgb0075
 in which R1 has the same significance as in claim 1 and the 4,6-(or 2,6-) dichloro-2-(or 4-) hydrazino-5-alkylthio pyrimidine thus obtained is condensed , mole for mole, with a compound of formula
Figure imgb0076
in which R2 and R3 have the same significance as in claim 1.
6. Process for the preparation of compounds of formula (I) of claim 1 in which one of the substituents X and Y is an
Figure imgb0077
group, and the other is a hydrazino group, characterised in that hydrazine is condensed, mole for mole, with a compound of formula:
Figure imgb0078
in which R1, R2 and R3 have the same significance as in claim 1.
7. Process for the preparation of compounds of formula (I) of claim 1 in which X and Y are both hydrazino groups, characterised in that hydrazine is condensed with a 2,4,6-trichloro-5-alkylthio pyrimidine of formula:
Figure imgb0079
in which R, has the same significance as in claim 1.
8. Application as herbicides and fungicides of the products defined in each of claims 1 to 3.
9. Herbicidal compositions containing 1 % to 95% by weight of a product such as that defined in each of claims 1 to 3, the complement to give 100% consisting of inert additives.
10. Herbicidal compositions containing 1 % to 80% by weight of a product such as that defined in each of claims 1 to 3, 80% to 1% by weight of another herbicide, the complement to give 100% consisting of inert additives.
EP19800400830 1979-06-20 1980-06-10 Hydrazino (or azido) 5-alkylthio pyrimidines, processes for their preparation and their uses as herbicides and fongicides Expired EP0021939B1 (en)

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FR7915769 1979-06-20
FR7915769A FR2459234A1 (en) 1979-06-20 1979-06-20 HYDRAZINO (OR AZIDO) ALKYLTHIO-5 PYRIMIDINES, PROCESSES FOR THEIR PREPARATION AND THEIR USES AS PESTICIDES

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